CN113603884A - Preparation method of non-isocyanate polyurethane - Google Patents
Preparation method of non-isocyanate polyurethane Download PDFInfo
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- CN113603884A CN113603884A CN202110903295.3A CN202110903295A CN113603884A CN 113603884 A CN113603884 A CN 113603884A CN 202110903295 A CN202110903295 A CN 202110903295A CN 113603884 A CN113603884 A CN 113603884A
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 63
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 239000012948 isocyanate Substances 0.000 title claims abstract description 39
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004593 Epoxy Substances 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 11
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 9
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 6
- 150000002924 oxiranes Chemical class 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- -1 tetrabutylammonium halide Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 125000004429 atom Chemical group 0.000 abstract description 5
- VVOAZFWZEDHOOU-UHFFFAOYSA-N magnolol Chemical compound OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 description 91
- 238000001228 spectrum Methods 0.000 description 43
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 description 17
- 239000011261 inert gas Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 229940016667 resveratrol Drugs 0.000 description 17
- 235000021283 resveratrol Nutrition 0.000 description 17
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- LUKBXSAWLPMMSZ-OWOJBTEDSA-N Trans-resveratrol Chemical compound C1=CC(O)=CC=C1\C=C\C1=CC(O)=CC(O)=C1 LUKBXSAWLPMMSZ-OWOJBTEDSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 125000005587 carbonate group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XZZXIYZZBJDEEP-UHFFFAOYSA-N imipramine hydrochloride Chemical compound [Cl-].C1CC2=CC=CC=C2N(CCC[NH+](C)C)C2=CC=CC=C21 XZZXIYZZBJDEEP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BYTORXDZJWWIKR-UHFFFAOYSA-N Hinokiol Natural products CC(C)c1cc2CCC3C(C)(CO)C(O)CCC3(C)c2cc1O BYTORXDZJWWIKR-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- FVYXIJYOAGAUQK-UHFFFAOYSA-N honokiol Chemical compound C1=C(CC=C)C(O)=CC=C1C1=CC(CC=C)=CC=C1O FVYXIJYOAGAUQK-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of non-isocyanate polyurethane, belonging to the technical field of organic synthesis. The method comprises the following steps: synthesis of bio-based epoxy: under the action of a phase transfer catalyst, obtaining a bio-based epoxide from bio-based polyphenol and epichlorohydrin; synthesizing bio-based five-membered cyclic carbonate: obtaining corresponding five-membered cyclic carbonate by bio-based epoxy and carbon dioxide under the action of a halogen bond donor catalyst; synthesis of non-isocyanate polyurethane: reacting the five-membered cyclic carbonate with diamine to obtain the non-isocyanate polyurethane. Compared with the existing isocyanate route, the method has the obvious advantages of cheap and easily-obtained raw materials, wide sources, green and mild synthesis route, high atom utilization rate, no metal residue and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing non-isocyanate polyurethane by utilizing bio-based polyphenol.
Background
Polyurethane, is the most popular polymer material because of its superior wear resistance, elasticity, durability, and toughness. Polyurethanes are used in a wide variety of applications in many areas, such as foams, footwear, coatings and paints, industrial machinery, adhesives, packaging and medical devices, and the like. By 2025, the Global polyurethane Market size is expected to reach $ 931 million according to the latest report by Global Market institute, with a composite annual growth rate of 5.8% during the prediction period. Since the 21 st century, the yield and sales of polyurethane in China are continuously and rapidly increased, the yield of polyurethane in China in 2019 reaches 1366 ten thousand tons, which accounts for about 45% of the total global yield, and the consumption of polyurethane products reaches 1185 ten thousand tons. China currently becomes the largest polyurethane producing country in the world and is one of the largest polyurethane markets.
In 1947, the bayer laboratory in germany gave polyurethanes for the first time by stepwise polyaddition of di-and polyisocyanates to short-and long-chain polyols. Since then, isocyanates and polyols become the main raw materials used in the industrial production of polyurethanes, and petroleum resources are the synthetic cornerstones of most polyurethanes. In the conventional polyurethane synthesis route, toxic phosgene is required as a raw material for synthesizing isocyanate, which not only causes environmental problems, but also the obtained isocyanate is harmful to human health. In terms of material properties, conventional polyurethanes have inherent disadvantages. The inclusion of water-labile bonds in the polymer structure makes such materials susceptible to environmental influences. Furthermore, the increasing consumption of petroleum resources has forced researchers to explore more sustainable, more atom efficient, greener and less toxic synthetic routes leading to so-called "non-isocyanate polyurethanes".
There are two main routes to the preparation of non-isocyanate polyurethanes. One is the polycondensation of biscarbonates with diamines or the polycondensation of biscarbamates with diols, resulting in predominantly linear polyurethanes. And the gradual addition polymerization of the multifunctional five-membered cyclic carbonate and diamine is not sensitive to water and air, no special careful storage is needed, no irreversible byproduct is formed, and the obtained polyurethane does not form volatile low-molecular-weight byproduct, so that the method has great industrial value.
The stepwise ring-opening polymerization process of preparing non-isocyanate polyurethane mainly relates to the synthesis of multifunctional five-membered cyclic carbonate. There are many methods for producing five-membered cyclic carbonates, and among them, a reaction for obtaining carbonates by cycloaddition of epoxides with carbon dioxide has been most popular in recent years and has been widely studied. In order to reduce the reaction conditions of the cycloaddition reaction, a great deal of research has been conducted on the development of a safe, efficient, low-loading, mild-condition catalyst, including a series of metal catalysts and organic catalysts represented by ammonium halide salts, phosphonium halide salts, imidazolium halide salts, and bifunctional catalytic systems. The organic catalyst is widely applied to the synthesis of cyclic carbonate due to the characteristics of low price and no metal residue, and the obtained carbonate can meet the requirements of microelectronics and biomedicine fields on metal residue. Recently, with the increasing exhaustion of petroleum resources, efforts are being made to develop biomass resources that are widely available in nature to replace non-renewable petroleum resources. The most used biomass resources are the botanicals, mainly from trees and crops. The raw materials are mainly divided into several different categories: lignocellulose, vegetable oils, starch and sugar.
In the previously disclosed patents and articles for preparing non-isocyanate polyurethanes, bisphenol A is often used as a raw material to prepare the corresponding epoxy and carbonate, which is then reacted with a diamine to prepare the polyurethane (ACS Sustainable chem. Eng.2020,8,1651-1658, CN107857879A, etc.). However, bisphenol a causes endocrine dyscrasia, and since 3/2/2011, the european union has prohibited the production of baby bottles containing bisphenol a, which may cause safety hazards. In addition, the diamines used in most patents and articles are simple diamines such as butanediamine, hexanediamine, etc. with relatively low molecular weight (ACS Sustainable chem. Eng.2019,7,20126-.
Disclosure of Invention
The invention aims to provide a green sustainable synthetic route for obtaining non-isocyanate polyurethane by using biomass resources as raw materials. The process allows the precise preparation of non-isocyanate polyurethanes.
A method for preparing non-isocyanate polyurethane from bio-based bicyclic carbonate comprises the following steps:
(1) synthesis of bio-based epoxy: under the action of a phase transfer catalyst, obtaining a bio-based epoxide from bio-based polyphenol and epichlorohydrin;
the bio-based phenol is shown as a formula (I)
HO-Ar-R1-Ar-OH
(I)
Wherein R is1Selected from linear alkyl with 0-2 carbon atoms; ar is selected from a benzene ring with a branched alkyl substituent group with 0-3 carbon atoms;
the phase transfer catalyst is tetrabutylammonium halide;
(2) synthesizing bio-based five-membered cyclic carbonate: obtaining corresponding five-membered cyclic carbonate from the bio-based epoxy obtained in the step (1) and carbon dioxide under the action of a halogen bond donor catalyst;
the halogen bond donor catalyst is shown as a formula (II)
Wherein R is2Selected from hydrogen, branched or straight chain alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, dimethylamino and pyrrolidinyl; x is selected from halogen;
(3) synthesis of non-isocyanate polyurethane: and (3) reacting the five-membered cyclic carbonate obtained in the step (2) with diamine to obtain the non-isocyanate polyurethane.
The diamine is shown as a formula (III)
H2N-R3-NH2
(III)
Wherein R is3The polyether is polyether with molecular weight of 200-2000 or alkyl with 36 carbon atoms.
The bio-based polyphenols are preferably of the following two structures: (A) magnolol; (B) resveratrol.
The epoxy used in the reaction is epichlorohydrin, and the structure of the epoxy is shown as the following formula:
the phase transfer catalyst used in the reaction is tetrabutyl ammonium halide salt, and the structure of the phase transfer catalyst is shown as the following formula:
wherein X is selected from chlorine, bromine and iodine.
Preferably, the halogen bond donor catalyst is as follows:
preferably, the halogen bond donor catalyst used in the reaction is 4-dimethylamino-N-iodopyridine bromide ([ DMAPI ] Br), and the structure is shown as the following formula:
preferably, the amine used in the ammonolysis reaction is polyetheramine D2000, polyetheramine D400, polyetheramine D230 or Priamine 1074.
Preferably, the reaction is carried out at 80-100 ℃ in the step (1), and after the reaction is finished, a sodium hydroxide aqueous solution is added, and the biological epoxy oxide is obtained by extraction, drying and filtration.
Preferably, in the step (2), the reaction temperature is 60-120 ℃, the reaction time is 12-24 hours, and the molar ratio of the bio-based epoxy to the halogen bond donor catalyst is 1: 0.01-1: 0.05.
preferably, the reaction temperature in the step (3) is 80-120 ℃, and the reaction time is 12-24 hours.
In the step (3), the mole ratio of the five-membered cyclic carbonate to the functional groups of the amino groups in the diamine is 1: 1. and (3) reacting the five-membered cyclic carbonate obtained in the step (2) with diamine according to the molar ratio of the carbonate to the amino functional groups to obtain the non-isocyanate polyurethane. For example, polyetheramine D230, with a molecular weight of 230, 1mol of polyetheramine D230 has 2mol of amino functions.
The method for preparing the non-isocyanate polyurethane by using the bio-based phenol preferably selects the reaction of two bio-based polyphenols of magnolol and resveratrol, and comprises the following specific steps:
(1) synthesis of bio-based epoxy: the bio-based polyphenol, epichlorohydrin and phase transfer catalyst tetrabutylammonium halide are mixed according to the weight ratio of 1: 4: 0.1-1: 12: 0.5, reacting at 80-100 ℃ for 3 hours, and cooling to room temperature after the reaction is finished. And dropwise adding a 40% sodium hydroxide aqueous solution by mass, and stirring for 3 hours. After completion, the mixture was poured into a separatory funnel, extracted three times with ethyl acetate and water, and the organic phase was collected and dried overnight with anhydrous sodium sulfate. After filtration to remove the sodium sulfate, the solvent was removed using a rotary evaporator to give the corresponding biobased epoxide.
The reaction formula of magnolol and resveratrol with epichlorohydrin and phase transfer catalyst tetrabutylammonium halide is as follows
(2) Synthesis of bio-based cyclic carbonate: and (2) using the bio-based epoxy obtained in the step (1) to further react with carbon dioxide to obtain the corresponding five-membered cyclic carbonate. The method comprises the following specific steps: bio-based epoxy is reacted with catalyst 4-dimethylamino-N-iodopyridine bromide ([ DMAPI ] Br) under inert gas according to 1: 0.01-1: 0.05 molar, adding a balloon of carbon dioxide, and stirring in an oil bath at 100 ℃ for 24 hours. After the reaction is finished, performing column chromatography by adopting a petroleum ether/ethyl acetate system or a dichloromethane system to obtain corresponding five-membered cyclic carbonate.
(3) Synthesis of a Biophenol-based non-isocyanate polyurethane: using the five-membered cyclic carbonate obtained in (2) under an inert gas according to the carbonate: amino group 1: 1-1: 1.2 the molar ratio of the functional groups was added and stirred at 100 ℃ for 24 hours to obtain a non-isocyanate polyurethane.
Has the advantages that:
(1) according to the invention, through the synthesis steps, the bio-based polyphenol (preferably magnolol and resveratrol) with wide sources is used as a raw material, the non-isocyanate polyurethane is successfully prepared, and compared with the isocyanate route widely used at present, the polyurethane has the characteristics of high atom utilization rate, high yield, no metal residue and wide application, and has great commercial application potential in the fields of biomedicine, microelectronics and the like with strict requirements on metal residue.
(2) The raw materials magnolol and resveratrol used in the invention are wide in source, cheap and easily available, and biomass resources are developed and utilized to a certain extent to replace petroleum resources.
(3) The halogen bond donor catalyst system used in the invention has the advantages of mildness, high efficiency, short reaction time and high conversion rate.
Compared with the existing isocyanate route, the method has the obvious advantages of cheap and easily-obtained raw materials, wide sources, green and mild synthetic route, high atom utilization rate, no metal residue and the like. The invention firstly provides a preparation route for synthesizing corresponding epoxy by using cheap and easily-obtained bio-based polyphenol as a raw material, then catalyzing the epoxy by using a halogen bond donor catalyst to perform cycloaddition reaction with carbon dioxide to obtain cyclic carbonate, and finally performing ammonolysis reaction with diamine to obtain non-isocyanate polyurethane. The used bio-based phenol has wide sources, high efficiency in reaction process, relatively mild reaction conditions and high atom utilization rate, meets the basic aim of green chemistry, and the obtained polyurethane has no metal residue and wide application.
Drawings
FIG. 1 is a hydrogen spectrum of resveratrol epoxide of example 1
FIG. 2 is a carbon spectrum of resveratrol epoxide in example 1
FIG. 3 is a hydrogen spectrum of resveratrol carbonate in example 1
FIG. 4 is a carbon spectrum of resveratrol carbonate in example 1
FIG. 5 shows the hydrogen spectra of the polyurethanes obtained from resveratrol carbonate and Priamine 1074 in example 1
FIG. 6 is a hydrogen spectrum of magnolol epoxide of examples 2 to 5
FIG. 7 is a carbon spectrum of magnolol epoxide of examples 2 to 5
FIG. 8 is a hydrogen spectrum of magnolol carbonate of examples 2 to 5
FIG. 9 is a carbon spectrum of magnolol carbonate of examples 2 to 5
FIG. 10 is a chart of the hydrogen spectra of the polyurethane obtained from magnolol carbonate and polyetheramine D2000 of example 2
FIG. 11 is a graph showing the infrared contrast of the polyurethane obtained from magnolol carbonate and polyetheramine D2000 of example 2
FIG. 12 is a chart of the hydrogen spectra of the polyurethane obtained from magnolol carbonate and polyetheramine D400 in example 3
FIG. 13 is a chart of the hydrogen spectra of the polyurethane obtained from magnolol carbonate and polyetheramine D230 in example 4
FIG. 14 shows the hydrogen spectra of the polyurethane obtained from honokiol carbonate and Priamine 1074 in example 5
FIG. 15 is a graph showing the IR contrast of the polyurethanes obtained from magnolol carbonate and primamine 1074 in example 5
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit of the invention and from the scope of the invention.
Example 1:
(1) resveratrol epoxy resinThe synthesis of (2): a50 mL Schlenk flask was charged with a rotor and operated anhydrous and anaerobic. Resveratrol (1.14g, 5mmol, 1eq), catalyst TBAB (0.16g, 0.5mmol, 0.1eq), and epichlorohydrin (4.7mL, 60mmol, 12eq) were added in sequence under inert gas, and an inert balloon was inserted as protection. The mixture was stirred in an oil bath at 80 ℃ for 3 hours, and then a 40% aqueous solution of sodium hydroxide was added thereto and the stirring was continued for 3 hours. After cooling to room temperature, the solid was removed by filtration, washed three times with deionized water, and dried to give 1.44g of a yellow oil. The hydrogen spectrum of the product is shown in figure 1, and the spectrum data is as follows:1h NMR (400MHz, Chloroform-d) δ 7.47-7.36 (m,2H),7.01(d, J ═ 16.3Hz,1H), 6.94-6.83 (m,3H),6.67(d, J ═ 2.2Hz,2H),6.41(t, J ═ 2.3Hz,1H),4.24(dd, J ═ 11.0,3.1Hz,3H),3.95(ddd, J ═ 11.0,5.7,2.2Hz,3H),3.36(ddd, J ═ 5.5,3.9,2.8Hz,3H),2.91(q, J ═ 4.9Hz,3H),2.76 (ddd, J ═ 4.9,2.7Hz,3H), 2.76 (ddc, J ═ 4.9,2.7, 3H), and the carbon data shown in fig. 2:13C NMR(101MHz,Chloroform-d)δ159.83,158.34,139.83,130.35,128.92,127.89,126.56,114.88,105.58,100.91,68.90,50.13,44.76.
(2) synthesizing resveratrol carbonate: adding a rotor into a 10mL Schlenk tube, carrying out anhydrous and anaerobic operation, and sequentially adding the resveratrol epoxy (0.79g, 2mmol, 1eq) obtained in (1) and a catalyst [ DMAPI ] under inert gas]Br (7mg, 0.02mmol, 0.01 eq). The balloon filled with carbon dioxide is used for pumping and changing air for three times, the carbon dioxide balloon is inserted, and the mixture is put into an oil bath pan with the temperature of 100 ℃ and stirred for 24 hours. After the reaction is finished, performing column chromatography by using a petroleum ether/ethyl acetate system to obtain the resveratrol carbonate which is a white solid. The hydrogen spectrum of the product is shown in figure 3, and the spectrum data is as follows:1h NMR (400MHz, Chloroform-d) δ 7.45(d, J ═ 8.6Hz,2H),7.03(d, J ═ 16.2Hz,1H), 6.93-6.84 (m,3H),6.70(d, J ═ 2.3Hz,2H), 6.44-6.32 (m,1H),5.05(dq, J ═ 8.9,3.7Hz,3H),4.64(t, J ═ 8.5Hz,3H),4.55(ddd, J ═ 8.5,5.8,4.9Hz,3H), 4.33-4.22 (m,3H), 4.21-3.85 (m,6H), carbon spectrum is shown in fig. 4, and the data are:13CNMR(101MHz,DMSO-d6)δ159.79,158.23,155.36,140.19,130.66,129.35,128.43,115.42,106.13,101.02,75.28,68.07,66.49.
(3) synthesis of non-isocyanate polyurethane based on resveratrol: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The resveratrol carbonate (38mg, 0.07mmol, 1eq) obtained in (2) and pramine 1074(28mg, 0.105mmol, 1.0eq) were added in succession under inert gas. The hydrogen spectrum of the product is shown in FIG. 5. The disappearance of the hydrogen from the five-membered carbonate ring indicates that the carbonate ring is opened and polyurethane is formed.
Example 2:
(1) and (3) synthesis of magnolol epoxy: a50 mL Schlenk flask was charged with a rotor and operated anhydrous and anaerobic. Under inert gas, magnolol (2.66g, 10mml, 1eq), catalyst TBAB (0.64g, 2mmol, 0.2eq) and epichlorohydrin (3.2mL, 40mmol, 4eq) were added in sequence, and stirred in an oil bath at 90 ℃ for 3 hours. After cooling, 1.2mL of a 40% sodium hydroxide solution was added and the mixture was stirred at room temperature for 3 hours. After the reaction, the reaction solution was poured into a separatory funnel, and extracted with ethyl acetate and water. The organic phase was collected and dried overnight with anhydrous sodium sulfate. Filtering to remove sodium sulfate, and spin-drying the filtrate to obtain magnolol epoxy. The hydrogen spectrum of the product is shown in fig. 6, and the spectrum data is as follows:1h NMR (400MHz, Chloroform-d) δ 7.14-7.06 (m,2H),6.89(d, J ═ 8.1Hz,1H),5.98(ddt, J ═ 16.8,10.0,6.7Hz,1H), 5.12-5.02 (m,2H),4.17(dt, J ═ 11.3,3.0Hz,1H),3.93(ddd, J ═ 11.1,7.4,5.2Hz,1H),3.36(dt, J ═ 6.7,1.6Hz,2H),3.19(ddtd, J ═ 5.5,4.1,2.8,1.1Hz,1H),2.75(ddd, J ═ 5.1,4.1,2.9, 1H),2.58(ddd, J ═ 5.1, 2.1, 2.9, 1H),2.58(ddd, 7.7 Hz,1H),2.7, 7, 7.2H, 7H, 2H:13C NMR(101MHz,Chloroform-d)δ154.46,137.81,132.51,131.84,128.48,128.23,115.59,112.81,69.17,50.40,44.55,39.43.
(2) synthesis of magnolol carbonate: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol epoxy (0.757g, 2mmol, 1eq) obtained in (1) and the catalyst, 4-pyrrolidinyl-N-iodopyridine bromide (14mg,0.04mmol,0.02eq), were added sequentially under inert gas. The balloon filled with carbon dioxide is used for pumping and changing air for three times, the carbon dioxide balloon is inserted, and the mixture is put into an oil bath pan with the temperature of 100 ℃ and stirred for 24 hours. After the reaction is finished, performing column chromatography by using a petroleum ether/ethyl acetate system to obtain the magnolol carbonate. The hydrogen spectrum of the product is shown in figure 8,the spectrogram data is as follows:1h NMR (400MHz, Chloroform-d) δ 7.14(dt, J ═ 8.3,2.1Hz,2H),7.01(dd, J ═ 4.1,2.3Hz,2H),6.84(dd, J ═ 8.4,1.7Hz,2H),5.97(ddt, J ═ 16.9,10.2,6.7Hz,2H),5.11 to 4.99(m,4H),4.83(ddq, J ═ 9.4,6.8,3.0Hz,2H),4.38 to 4.19(m,4H),4.01 to 3.81(m,2H),3.36(d, J ═ 6.7Hz,4H), the carbon spectrum of the product is shown in fig. 9, and the data are:13C NMR(101MHz,Chloroform-d)δ154.76,153.62,153.56,137.72,131.23,128.91,128.13,115.75,112.20,74.44,65.63,39.33.
(3) synthesis of non-isocyanate polyurethane based on magnolol: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol carbonate (0.425g, 0.91mmol, 1eq) obtained in (2) and polyetheramine D2000(1.8mL, 0.91mmol, 1eq) were added in succession under inert gas. The mixture was stirred in an oil bath at 100 ℃ for 24 hours to obtain a non-isocyanate polyurethane. The hydrogen spectrum of the product is shown in FIG. 10. Disappearance of hydrogen on carbonate five-membered ring at 4.2-4.4ppm in the spectrum, and 1716cm in infrared spectrum-1The formation of urethane groups (as shown in fig. 11) indicates that the carbonate ring is opened, resulting in polyurethane.
Example 3:
(1) and (3) synthesis of magnolol epoxy: a50 mL Schlenk flask was charged with a rotor and operated anhydrous and anaerobic. Under inert gas, magnolol (2.66g, 10mml, 1eq), catalyst TBAB (1.29g, 4mmol, 0.4eq) and epichlorohydrin (6.4mL, 80mmol, 8eq) were added in sequence, and stirred in an oil bath at 80 ℃ for 3 hours. After cooling, 1.2mL of a 40% sodium hydroxide solution was added and the mixture was stirred at room temperature for 3 hours. After the reaction, the reaction solution was poured into a separatory funnel, and extracted with ethyl acetate and water. The organic phase was collected and dried overnight with anhydrous sodium sulfate. Filtering to remove sodium sulfate, and spin-drying the filtrate to obtain magnolol epoxy. The hydrogen spectra and the hydrogen spectra of the product are shown in FIGS. 6 and 7.
(2) Synthesis of magnolol carbonate: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol epoxy (0.757g, 2mmol, 1eq) obtained in (1) and the catalyst, 4-methoxy-N-iodopyridine bromide (25mg,0.08mmol,0.04eq), were added sequentially under inert gas. The balloon filled with carbon dioxide is used for pumping and changing air for three times, the carbon dioxide balloon is inserted, and the mixture is put into an oil bath pan with the temperature of 100 ℃ and stirred for 24 hours. After the reaction is finished, performing column chromatography by using a petroleum ether/ethyl acetate system to obtain the magnolol carbonate. The hydrogen spectra and the hydrogen spectra of the product are shown in FIGS. 8 and 9.
(3) Synthesis of non-isocyanate polyurethane based on magnolol: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol carbonate (0.186g, 0.4mmol, 1eq) obtained in (2) and polyetheramine D400(0.16g, 0.4mmol, 1eq) were added in succession under inert gas. The mixture was stirred in an oil bath at 100 ℃ for 24 hours to obtain a non-isocyanate polyurethane. The hydrogen spectrum of the product is shown in FIG. 12. The disappearance of hydrogen from the five-membered carbonate ring at 4.2-4.4ppm in the spectrum indicates that the carbonate ring is opened and polyurethane is formed.
Example 4:
(1) and (3) synthesis of magnolol epoxy: a50 mL Schlenk flask was charged with a rotor and operated anhydrous and anaerobic. Under inert gas, magnolol (2.66g, 10mml, 1eq), catalyst TBAB (1.61g, 5mmol, 0.5eq) and epichlorohydrin (7.8mL, 100mmol, 10eq) were added in sequence, and the mixture was stirred in an oil bath at 100 ℃ for 3 hours. After cooling, a sodium hydroxide solution with the mass fraction of 40% is added, and the mixture is stirred for 3 hours at room temperature. After the reaction, the reaction solution was poured into a separatory funnel, and extracted with ethyl acetate and water. The organic phase was collected and dried overnight with anhydrous sodium sulfate. Filtering to remove sodium sulfate, and spin-drying the filtrate to obtain magnolol epoxy. The hydrogen spectrum and carbon spectrum of the product are shown in FIGS. 6 and 7.
(2) Synthesis of magnolol carbonate: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol epoxy (0.757g, 2mmol, 1eq) obtained in (1) and the catalyst N-iodopyridine bromide (28mg,0.1mmol,0.05eq) were added sequentially under inert gas. The balloon filled with carbon dioxide is used for pumping and changing air for three times, the carbon dioxide balloon is inserted, and the mixture is put into an oil bath pan with the temperature of 100 ℃ and stirred for 24 hours. After the reaction is finished, performing column chromatography by using a petroleum ether/ethyl acetate system to obtain the magnolol carbonate. The hydrogen spectrum and carbon spectrum of the product are shown in FIGS. 8 and 9.
(3) Synthesis of non-isocyanate polyurethane based on magnolol: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol carbonate (0.425g, 0.91mmol, 1eq) obtained in (2) and polyetheramine D230(0.092g, 0.4mmol, 1.0eq) were added in succession under inert gas. The mixture was stirred in an oil bath at 100 ℃ for 24 hours to obtain a non-isocyanate polyurethane. The hydrogen spectrum of the product is shown in FIG. 13. The disappearance of hydrogen from the five-membered carbonate ring at 4.2-4.4ppm in the spectrum indicates that the carbonate ring is opened and polyurethane is formed.
Example 5:
(1) and (3) synthesis of magnolol epoxy: a50 mL Schlenk flask was charged with a rotor and operated anhydrous and anaerobic. Under inert gas, magnolol (2.66g, 10mml, 1eq), catalyst TBAB (1.61g, 5mmol, 0.5eq) and epichlorohydrin (7.8mL, 100mmol, 10eq) were added in sequence, and the mixture was stirred in an oil bath at 100 ℃ for 3 hours. After cooling, a sodium hydroxide solution with the mass fraction of 40% is added, and the mixture is stirred for 3 hours at room temperature. After the reaction, the reaction solution was poured into a separatory funnel, and extracted with ethyl acetate and water. The organic phase was collected and dried overnight with anhydrous sodium sulfate. Filtering to remove sodium sulfate, and spin-drying the filtrate to obtain magnolol epoxy. The hydrogen spectrum and carbon spectrum of the product are shown in FIGS. 6 and 7.
(2) Synthesis of magnolol carbonate: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol epoxy (0.757g, 2mmol, 1eq) obtained in (1) and the catalyst [ DMAPI ] Br (33mg, 0.1mmol,0.05eq) were added in succession under inert gas. The balloon filled with carbon dioxide is used for pumping and changing air for three times, the carbon dioxide balloon is inserted, and the mixture is put into an oil bath pan with the temperature of 100 ℃ and stirred for 24 hours. After the reaction is finished, performing column chromatography by using a petroleum ether/ethyl acetate system to obtain the magnolol carbonate. The hydrogen spectrum and carbon spectrum of the product are shown in FIGS. 8 and 9.
(3) Synthesis of non-isocyanate polyurethane based on magnolol: a10 mL Schlenk tube was charged with a rotor and operated anhydrous and anaerobic. The magnolol carbonate (0.186g, 0.4mmol, 1.0eq) and the pramine 1074(0.13g, 1.2eq) obtained in (2) were added in this order under an inert gas atmosphere. The mixture was stirred in an oil bath at 100 ℃ for 24 hours to obtain a non-isocyanate polyurethane. The product has a hydrogen spectrum such asAs shown in fig. 14. The opening of the carbonate ring is indicated in the spectrum by the disappearance of hydrogen from the five-membered ring of the carbonate at 4.2 to 4.4 ppm. Furthermore, it was found in the IR spectrum (FIG. 15) at 1700cm-1The peak of stretching vibration of the carbonyl group in the urethane was observed, and it was confirmed that polyurethane was produced.
Claims (10)
1. A preparation method of non-isocyanate polyurethane is characterized by comprising the following steps: comprises the following steps:
(1) synthesis of bio-based epoxy: under the action of a phase transfer catalyst, obtaining a bio-based epoxide from bio-based polyphenol and epichlorohydrin;
the bio-based phenol is shown as a formula (I)
HO-Ar-R1-Ar-OH
(I)
Wherein R is1Selected from linear alkyl with 0-2 carbon atoms; ar is selected from a benzene ring with a branched alkyl substituent group with 0-3 carbon atoms;
the phase transfer catalyst is tetrabutylammonium halide;
(2) synthesizing bio-based five-membered cyclic carbonate: obtaining corresponding five-membered cyclic carbonate from the bio-based epoxy obtained in the step (1) and carbon dioxide under the action of a halogen bond donor catalyst;
the halogen bond donor catalyst is shown as a formula (II)
Wherein R is2Selected from hydrogen, branched or straight chain alkyl with 1-3 carbon atoms, alkoxy with 1-3 carbon atoms, dimethylamino and pyrrolidinyl; x is selected from halogen;
(3) synthesis of non-isocyanate polyurethane: and (3) reacting the five-membered cyclic carbonate obtained in the step (2) with diamine to obtain the non-isocyanate polyurethane.
The diamine is shown as a formula (III)
H2N-R3-NH2
(III)
Wherein R is3The polyether is polyether with molecular weight of 200-2000 or alkyl with 36 carbon atoms.
2. The method of claim 1, wherein: the phase transfer catalyst is tetrabutylammonium bromide.
3. The method of claim 1, wherein: the halogen bond donor catalyst is as follows:
4. the production method according to claim 3, characterized in that: the halogen bond donor catalyst is 4-dimethylamino-N-iodopyridine bromide
5. The method of claim 1, wherein: the molar ratio of the bio-based phenol to the epichlorohydrin to the phase transfer catalyst is 1: 4: 0.1-1: 12: 0.5.
6. the method of claim 1, wherein: and (2) reacting at 80-100 ℃, adding a sodium hydroxide aqueous solution after the reaction is finished, extracting, drying and filtering to obtain the bio-based epoxide.
7. The method of claim 1, wherein: and (3) the diamine in the step (3) is polyether amine D2000, polyether amine D400, polyether amine D230 or Priamine 1074.
8. The method of claim 1, wherein: in the step (2), the reaction temperature is 60-120 ℃, the reaction time is 12-24 hours, the molar ratio of the bio-based epoxy to the halogen bond donor catalyst is 1: 0.01-1: 0.05.
9. the method of claim 1, wherein: in the step (3), the mole ratio of the five-membered cyclic carbonate to the functional groups of the amino groups in the diamine is 1: 1.
10. the method of claim 1, wherein: in the step (3), the reaction temperature is 80-120 ℃, and the reaction time is 12-24 hours.
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